JP2018028115A - Agent and method for repairing plating base material, and plating base material - Google Patents
Agent and method for repairing plating base material, and plating base material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- Mechanical Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本発明は、金属基材の表面にめっき層を有するめっき基材の修復剤および修復方法ならびにめっき基材に関する。 The present invention relates to a repairing agent and repairing method for a plating base material having a plating layer on the surface of a metal base material, and a plating base material.
自動車部品としては、鋼板の表面に亜鉛めっき層を形成した亜鉛めっき鋼板が一般的に使用されている。亜鉛めっき層に含まれる亜鉛は、鋼板に含まれる鉄よりも高いイオン化傾向を示す。このため、亜鉛めっき層に引っかき傷（スクラッチ）が形成されて鋼板が露出したとき、亜鉛めっき層は亜鉛が溶出する犠牲防食性能および当該溶出した亜鉛が露出鋼板の表面に皮膜を形成する保護皮膜形成能を有し、自己修復を行い、耐食性を発揮する。しかしながら、従来の亜鉛めっき鋼板は十分な耐食性を発揮できなかった。 As an automobile part, a galvanized steel sheet in which a galvanized layer is formed on the surface of the steel sheet is generally used. Zinc contained in the galvanized layer shows a higher ionization tendency than iron contained in the steel plate. For this reason, when a scratch is formed in the galvanized layer and the steel sheet is exposed, the galvanized layer has a sacrificial anticorrosive performance in which zinc elutes and a protective film in which the eluted zinc forms a film on the surface of the exposed steel sheet Has the ability to form, self-repairs, and exhibits corrosion resistance. However, the conventional galvanized steel sheet cannot exhibit sufficient corrosion resistance.
そこで、特許文献１には、金属基体表面に設けられる防食被膜であって、導電性微粒子からなる下地部と、導電性高分子からなる表面部とを有する防食被膜が報告されている。しかしながら、このような技術においても、やはり十分な耐食性が発揮されるとは言えないのが現状である。 Therefore, Patent Document 1 reports an anticorrosion coating provided on the surface of a metal substrate, which has a base portion made of conductive fine particles and a surface portion made of a conductive polymer. However, even in such a technique, it cannot be said that sufficient corrosion resistance is exhibited.
本発明の発明者等は、保護皮膜への修復剤の添加を試みたところ、あらゆる化合物を単成分で添加してみても、十分な耐食性は得られないという新たな問題を見出した。 The inventors of the present invention tried to add a restorative agent to the protective film, and found a new problem that sufficient corrosion resistance could not be obtained even when all compounds were added as a single component.
自動車の軽量化には、ハイテン材料（高張力鋼板）などの鋼板が有用である。このような鋼板表面にめっき層を有するめっき基材は、他の鋼板を用いためっき基材よりも、腐食に対して鋭敏に水素脆性および強度低下をもたらすため、上記の問題はより深刻であった。 Steel plates such as high-tensile materials (high-tensile steel plates) are useful for reducing the weight of automobiles. The plating base having a plating layer on the surface of such a steel plate is more sensitive to corrosion than the plating base material using other steel plates and causes hydrogen embrittlement and a decrease in strength. It was.
本発明は、より十分な耐食性を示す修復剤を提供することを目的とする。 An object of this invention is to provide the restoration | repair agent which shows more sufficient corrosion resistance.
本発明は、金属基材の表面に、該金属基材を構成する金属よりもイオン化傾向が高い金属を含有するめっき層を有するめっき基材のための修復剤であって、
リン酸化合物およびホスホン酸化合物を含む修復剤に関する。
The present invention is a restoration agent for a plating substrate having a plating layer containing a metal having a higher ionization tendency than the metal constituting the metal substrate on the surface of the metal substrate,
The present invention relates to a restoration agent comprising a phosphoric acid compound and a phosphonic acid compound.
本発明の修復剤は、より十分な耐食性を示す。詳しくは本発明の修復剤は、実使用環境下でめっき基材に金属基材に達する引っかき傷（スクラッチ）が形成されても、犠牲防食性能および保護皮膜形成能に優れているため、良好な自己修復性を有し、より十分な耐食性を発揮する。
本発明の修復剤は、金属基材としてハイテン材料（高張力鋼板）を用いた場合に特に有用である。
The restoration agent of the present invention exhibits more sufficient corrosion resistance. Specifically, the restoration agent of the present invention is excellent in sacrificial anticorrosion performance and protective film forming ability even when scratches (scratches) reaching the metal substrate are formed on the plating substrate in an actual use environment. Has self-healing properties and exhibits more sufficient corrosion resistance.
The restoration agent of the present invention is particularly useful when a high-tensile material (high-tensile steel plate) is used as the metal substrate.
［修復剤］
本発明の修復剤は、めっき基材のためのものであり、めっき基材のめっき層表面から金属基材に達する欠陥が形成されたとき、欠陥の内側表面、特に露出した金属基材の表面に保護皮膜を形成する。以下、本発明を、図面を用いて詳しく説明するが、図面における各種の要素は、本発明の理解のために模式的かつ例示的に示したにすぎず、外観および寸法比などは実物と異なり得る。本明細書で直接的または間接的に用いる“上下方向”、“左右方向”および“表裏方向”はそれぞれ、図中における上下方向、左右方向および表裏方向に対応した方向に相当する。特記しない限り、同じ符号または記号は、同じ部材または同じ意味内容を示すものとする。
[Restoration agent]
The restoration agent of the present invention is for a plating substrate, and when a defect reaching the metal substrate from the plating layer surface of the plating substrate is formed, the inner surface of the defect, particularly the exposed metal substrate surface A protective film is formed on the surface. Hereinafter, the present invention will be described in detail with reference to the drawings, but various elements in the drawings are merely schematically and exemplarily for understanding the present invention, and the appearance and dimensional ratio are different from the actual ones. obtain. The “vertical direction”, “left / right direction”, and “front / back direction” used directly or indirectly in this specification correspond to directions corresponding to the vertical direction, left / right direction, and front / back direction in the drawing, respectively. Unless otherwise specified, the same symbols or symbols indicate the same members or the same meaning.
めっき基材１０は、図１に示すように、金属基材１および当該金属基材表面に形成されためっき層２を有する。金属基材１は、金属を含むあらゆる基材であってよく、通常、鉄を含み、所望により、炭素、ケイ素、マンガン、リン、硫黄等を含んでもよい。金属基材において、炭素の含有量は１重量％以下、特に０．８重量％以下であり、ケイ素、マンガン、リン、硫黄等の含有量はそれぞれ０．５重量％以下、特に０．３重量％以下であり、残部が鉄である。 As shown in FIG. 1, the plating substrate 10 includes a metal substrate 1 and a plating layer 2 formed on the surface of the metal substrate. The metal substrate 1 may be any substrate containing a metal, and usually contains iron, and may contain carbon, silicon, manganese, phosphorus, sulfur and the like as desired. In the metal substrate, the carbon content is 1% by weight or less, particularly 0.8% by weight or less, and the content of silicon, manganese, phosphorus, sulfur, etc. is 0.5% by weight or less, particularly 0.3% by weight, respectively. %, And the balance is iron.
金属基材１としては、自動車部品の分野においては、鋼板が好ましく、より好ましくはいわゆる炭素鋼板、特に高張力鋼板（ハイテン材料）である。 The metal substrate 1 is preferably a steel plate in the field of automobile parts, more preferably a so-called carbon steel plate, particularly a high-tensile steel plate (high-tensile material).
めっき層２は、金属基材１を構成する金属よりもイオン化傾向が高い金属を主成分として含有する。めっき層の主成分として含有される当該イオン化傾向が高い金属を、以下、「イオン化傾向が高い金属Ａ」ということがある。金属基材１が鋼板である場合、金属基材１を構成する金属とは鉄のことである。鉄よりもイオン化傾向が高い金属として、例えば、亜鉛、アルミニウムおよびマグネシウムからなる群から選択される１種以上の金属が挙げられる。好ましくは亜鉛である。このようなめっき層２に含有されるイオン化傾向が高い金属Ａは通常、イオンの形態で、後で詳述する保護皮膜の形成に寄与する。 The plating layer 2 contains a metal whose ionization tendency is higher than that of the metal constituting the metal substrate 1 as a main component. The metal having a high ionization tendency that is contained as the main component of the plating layer may be hereinafter referred to as “metal A having a high ionization tendency”. When the metal substrate 1 is a steel plate, the metal constituting the metal substrate 1 is iron. Examples of the metal having a higher ionization tendency than iron include one or more metals selected from the group consisting of zinc, aluminum, and magnesium. Zinc is preferable. The metal A having a high ionization tendency contained in the plating layer 2 is usually in the form of ions and contributes to the formation of a protective film described in detail later.
めっき層２は、金属基材１の露出表面での保護皮膜の形成の観点から、亜鉛めっき層であることが好ましい。亜鉛めっき層とは、亜鉛を含むめっき層のことであり、好ましくは亜鉛合金層である。 The plating layer 2 is preferably a galvanized layer from the viewpoint of forming a protective film on the exposed surface of the metal substrate 1. The zinc plating layer is a plating layer containing zinc, and preferably a zinc alloy layer.
めっき層２の形成方法としては、あらゆるめっき法を採用してもよく、例えば、いわゆる電気めっき法、無電解めっき法および溶融めっき法等の湿式めっき法；ならびにいわゆる真空めっき法（物理気相成長法（ＰＶＤ法））、化学蒸着法（ＣＶＤ法）および衝撃めっき法等の乾式めっき法が挙げられる。好ましくは乾式めっき法、特に衝撃めっき法である。衝撃めっき法は、中心部（例えば鉄核）の外殻部にめっき層の構成金属粒子を有する複合粒子を被処理物（金属基材１）に投射することにより、めっき層（皮膜）を形成する方法である。図１において、めっき層２が衝撃めっき法により形成され、めっき層２の内部において構成金属粒子２１の界面および間隙が存在するめっき基材の概略断面図が示されているが、めっき層は他の方法により形成されて、構成金属粒子の界面および間隙が存在しない形態を有していてもよい。 As a method for forming the plating layer 2, any plating method may be employed. For example, a so-called electroplating method, electroless plating method, hot plating method such as a hot dipping method, and so-called vacuum plating method (physical vapor deposition). Method (PVD method)), chemical vapor deposition (CVD), and impact plating. A dry plating method, particularly an impact plating method is preferred. In the impact plating method, a plating layer (film) is formed by projecting composite particles having metal particles constituting the plating layer on the outer shell of the central portion (for example, iron core) onto the object to be processed (metal substrate 1). It is a method to do. In FIG. 1, a schematic cross-sectional view of a plating substrate in which the plating layer 2 is formed by impact plating and the interfaces and gaps of the constituent metal particles 21 exist inside the plating layer 2 is shown. It may be formed by the method described above and have a form in which there are no interfaces and gaps between the constituent metal particles.
めっき層２の厚みは特に限定されず、例えば、１μｍ以上であってもよく、通常は１〜５０μｍ、特に１〜１０μｍである。 The thickness of the plating layer 2 is not particularly limited, and may be, for example, 1 μm or more, and is usually 1 to 50 μm, particularly 1 to 10 μm.
本発明の修復剤はリン酸化合物およびホスホン酸化合物を含む。修復剤とは、金属基材の露出表面に保護皮膜を形成する薬剤のことである。 The restorative agent of the present invention includes a phosphoric acid compound and a phosphonic acid compound. The restoration agent is an agent that forms a protective film on the exposed surface of the metal substrate.
リン酸化合物は、リン酸（Ｈ３ＰＯ４）およびリン酸塩からなる群から選択される１種以上の無機系リン酸化合物である。保護皮膜の形成の観点から好ましくはリン酸塩である。リン酸塩とは、第１リン酸イオン（Ｈ２ＰＯ４ −）、第２リン酸イオン（ＨＰＯ４ ２−）または第３リン酸イオン（ＰＯ４ ３−）等のリン酸イオンと、陽イオンとの塩のことである。保護皮膜の形成の観点から好ましいリン酸イオンは第１リン酸イオン、第２リン酸イオンであり、より好ましくは第１リン酸イオンである。陽イオンは、１価金属イオン、２価金属イオン、３価金属イオンおよびアンモニウムイオンからなる群から選択される１種以上のイオンである。好ましくは１価金属イオンおよびアンモニウムイオンである。１価金属イオンを構成する金属としてはアルカリ金属（例えば、ナトリウム、カリウム、リチウム）が挙げられ、好ましくはナトリウム、カリウムである。２価金属イオンを構成する金属としてはアルカリ土類金属（例えば、マグネシウム、カルシウム、ストロンチウム、バリウム）およびマンガンが挙げられ、好ましくはカルシウム、バリウムおよびマンガンである。３価金属イオンを構成する金属としては、例えば、クロム、アルミニウムが挙げられ、好ましくはクロムである。 The phosphate compound is one or more inorganic phosphate compounds selected from the group consisting of phosphoric acid (H 3 PO 4 ) and phosphate. From the viewpoint of forming a protective film, a phosphate is preferable. The phosphate is a phosphate ion such as a first phosphate ion (H 2 PO 4 − ), a second phosphate ion (HPO 4 2− ), or a third phosphate ion (PO 4 3− ), and a positive ion. It is a salt with ions. From the viewpoint of forming the protective film, preferred phosphate ions are a first phosphate ion and a second phosphate ion, and more preferably a first phosphate ion. The cation is one or more ions selected from the group consisting of monovalent metal ions, divalent metal ions, trivalent metal ions and ammonium ions. Preferred are monovalent metal ions and ammonium ions. Examples of the metal constituting the monovalent metal ion include alkali metals (for example, sodium, potassium and lithium), preferably sodium and potassium. Examples of the metal constituting the divalent metal ion include alkaline earth metals (eg, magnesium, calcium, strontium, barium) and manganese, preferably calcium, barium and manganese. As a metal which comprises a trivalent metal ion, chromium and aluminum are mentioned, for example, Preferably it is chromium.
保護皮膜の形成の観点から好ましいリン酸化合物の具体例として、例えば、リン酸（Ｈ３ＰＯ４）、リン酸二水素ナトリウム、リン酸二水素カリウム、リン酸二水素アンモニウム、リン酸二水素カルシウム、リン酸二水素バリウム、リン酸二水素マンガン、リン酸二水素リチウム、リン酸水素アンモニウムナトリウム、リン酸水素二アンモニウム、リン酸水素二カリウム、リン酸水素二ナトリウム、リン酸水素バリウム、リン酸水素マンガン（II）、リン酸クロム（III）、リン酸三カリウム、リン酸三ナトリウム、および縮合リン酸化合物が挙げられる。縮合リン酸化合物は、例えば、トリポリリン酸、ピロリン酸、メタリン酸、亜リン酸等の陰イオンと陽イオンからなる化合物であり、当該陽イオンは、例えば、アルカリ金属イオン、アルカリ土類金属イオンおよび両性金属イオン（亜鉛イオン、アルミニウムイオン）から選択される。 Specific examples of preferred phosphoric acid compounds from the viewpoint of forming a protective film include, for example, phosphoric acid (H 3 PO 4 ), sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, calcium dihydrogen phosphate. , Barium dihydrogen phosphate, manganese dihydrogen phosphate, lithium dihydrogen phosphate, sodium ammonium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, barium hydrogen phosphate, phosphoric acid Mention may be made of manganese hydrogen (II), chromium (III) phosphate, tripotassium phosphate, trisodium phosphate, and condensed phosphate compounds. The condensed phosphoric acid compound is, for example, a compound composed of an anion and a cation such as tripolyphosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, etc., and the cation includes, for example, an alkali metal ion, an alkaline earth metal ion, and It is selected from amphoteric metal ions (zinc ions, aluminum ions).
保護皮膜の形成の観点からより好ましいリン酸化合物としては、リン酸二水素ナトリウム、リン酸二水素カリウム、リン酸二水素アンモニウム、リン酸水素アンモニウムナトリウム、リン酸水素二アンモニウム、リン酸水素二カリウム、リン酸水素二ナトリウム、リン酸三ナトリウム、縮合リン酸化合物が挙げられる。好ましい縮合リン酸化合物の具体例として、例えば、トリポリリン酸二水素アルミニウム、トリポリリン酸カルシウム、トリポリリン酸亜鉛、トリポリリン酸ナトリウム、メタリン酸カルシウム、メタリン酸カルシウム、ピロリン酸カルシウム、ピロリン酸カルシウム、亜リン酸アルミニウム、亜リン酸亜鉛等が挙げられる。 More preferable phosphoric acid compounds from the viewpoint of forming a protective film include sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, sodium ammonium hydrogen phosphate, diammonium hydrogen phosphate, and dipotassium hydrogen phosphate. , Disodium hydrogen phosphate, trisodium phosphate, and condensed phosphate compounds. Specific examples of preferred condensed phosphate compounds include, for example, aluminum trihydrogenphosphate, calcium tripolyphosphate, zinc tripolyphosphate, sodium tripolyphosphate, calcium metaphosphate, calcium metaphosphate, calcium pyrophosphate, calcium pyrophosphate, aluminum phosphite, zinc phosphite Etc.
リン酸化合物は市販品として容易に入手可能である。リン酸化合物として２種以上の化合物を使用してもよい。 Phosphoric acid compounds are readily available as commercial products. Two or more compounds may be used as the phosphoric acid compound.
ホスホン酸化合物は、保護皮膜の金属基材１への吸着に寄与する非共有電子対を有する原子を含有するものであれば特に限定されず、例えば、窒素含有ホスホン酸化合物およびその塩からなる群から選択される１種以上の有機系ホスホン酸化合物である。有機系ホスホン酸化合物とは有機基およびホスホノ基を有する化合物という意味である。有機基としては、アルキレン基が挙げられ、特に炭素原子数１〜３のアルキレン基が好ましい。ホスホノ基は−Ｐ（＝Ｏ）（ＯＨ）２で表され、塩形態を有していてもよい。ホスホノ基が塩形態を有するとは、ホスホノ基の水酸基における水素イオンが遊離して、金属イオン等に置換されてもよいという意味である。金属イオンとして、例えば、ナトリウムイオン、カリウムイオン、カルシウムイオンが挙げられる。 The phosphonic acid compound is not particularly limited as long as it contains an atom having an unshared electron pair that contributes to the adsorption of the protective film to the metal substrate 1, and for example, a group consisting of a nitrogen-containing phosphonic acid compound and a salt thereof One or more organic phosphonic acid compounds selected from: The organic phosphonic acid compound means a compound having an organic group and a phosphono group. Examples of the organic group include an alkylene group, and an alkylene group having 1 to 3 carbon atoms is particularly preferable. The phosphono group is represented by —P (═O) (OH) 2 and may have a salt form. The phosphono group having a salt form means that a hydrogen ion at the hydroxyl group of the phosphono group may be released and substituted with a metal ion or the like. Examples of the metal ion include sodium ion, potassium ion, and calcium ion.
窒素含有ホスホン酸化合物としては、窒素原子およびホスホノ基を含有する有機化合物であれば特に限定されず、例えば、アミノトリス（メチレンホスホン酸）（ＡＴＭＰ）（構造式：Ｎ［ＣＨ２ＰＯ（ＯＨ）２］３）、アミノトリス（エチレンホスホン酸）（構造式：Ｎ［ＣＨ２ＣＨ２ＰＯ（ＯＨ）２］３）、およびこれらの金属塩等のホスホノ基含有アミンが挙げられる。金属塩は、当該化合物が１分子中、２個以上の水酸基を有する場合、一部の水酸基における水素イオンが金属イオンに置換されたものであってもよいし、または全ての水酸基における水素イオンが金属イオンに置換されたものであってもよい。 The nitrogen-containing phosphonic acid compound is not particularly limited as long as it is an organic compound containing a nitrogen atom and a phosphono group. For example, aminotris (methylenephosphonic acid) (ATMP) (structural formula: N [CH 2 PO (OH)) 2 ] 3 ), aminotris (ethylene phosphonic acid) (structural formula: N [CH 2 CH 2 PO (OH) 2 ] 3 ), and phosphono group-containing amines such as metal salts thereof. In the case where the compound has two or more hydroxyl groups in one molecule, the metal salt may be one in which hydrogen ions at some hydroxyl groups are replaced with metal ions, or hydrogen ions at all hydroxyl groups are present. It may be substituted with a metal ion.
ホスホン酸化合物は市販品として容易に入手可能である。ホスホン酸化合物として２種以上の化合物を使用してもよい。 The phosphonic acid compound is easily available as a commercial product. Two or more compounds may be used as the phosphonic acid compound.
リン酸化合物およびホスホン酸化合物は通常、１０／９０〜９０／１０の重量割合で含まれ、保護皮膜の形成の観点から好ましくは２０／８０〜８０／２０、より好ましくは４０／６０〜８０／２０、さらに好ましくは５５／４５〜７５／２５の重量割合で含まれる。リン酸化合物として２種以上の化合物を使用する場合、それらの合計量が上記範囲内であればよい。ホスホン酸化合物として２種以上の化合物を使用する場合、それらの合計量が上記範囲内であればよい。 The phosphoric acid compound and the phosphonic acid compound are usually contained in a weight ratio of 10/90 to 90/10, and preferably 20/80 to 80/20, more preferably 40/60 to 80 / from the viewpoint of forming a protective film. 20, More preferably, it is contained in a weight ratio of 55/45 to 75/25. When using 2 or more types of compounds as a phosphoric acid compound, those total amounts should just be in the said range. When using 2 or more types of compounds as a phosphonic acid compound, those total amounts should just be in the said range.
本発明の修復剤がリン酸化合物およびホスホン酸化合物を組み合わせて含有することにより、欠陥の形成により露出した金属基材表面に、非導電性および密着性に優れた保護皮膜を形成することができる。これらの結果、耐食性がより十分に向上するものと考えられる。リン酸化合物の代わりに、硝酸化合物、炭酸化合物、炭酸水素化合物、クロム酸化合物、ケイ酸化合物、フッ化金属、金属酸化物等の化合物を用いても、またはホスホン酸化合物の代わりに、芳香族または脂肪族カルボン酸または有機アミンを用いても、保護皮膜は形成されないか、または形成されたとしても、保護皮膜の非導電性または密着性の少なくとも一方が低下するため、十分な耐食性は得られない。本明細書中、非導電性とは、体積抵抗率が１０１２Ω・ｃｍ以上である絶縁性のことである。 When the restoration agent of the present invention contains a phosphoric acid compound and a phosphonic acid compound in combination, a protective film excellent in non-conductivity and adhesion can be formed on the surface of the metal substrate exposed by the formation of defects. . As a result, it is considered that the corrosion resistance is more sufficiently improved. Instead of phosphoric acid compounds, compounds such as nitric acid compounds, carbonic acid compounds, hydrogen carbonate compounds, chromic acid compounds, silicic acid compounds, metal fluorides, metal oxides, or aromatic compounds can be used instead of phosphonic acid compounds. Even when an aliphatic carboxylic acid or an organic amine is used, a protective film is not formed, or even if it is formed, at least one of the non-conductive property or the adhesive property of the protective film is lowered, so that sufficient corrosion resistance is obtained. Absent. In the present specification, the term “nonconductive” refers to an insulating property having a volume resistivity of 10 12 Ω · cm or more.
保護皮膜の形成時において、リン酸化合物のリン酸イオンは、めっき層に含まれる前記イオン化傾向が高い金属Ａのイオンとの反応（例えば、下記概略反応式（Ｉ））により、皮膜の主要骨格成分として非導電性化合物を生成する。他方、ホスホン酸化合物は、前記イオン化傾向が高い金属Ａのイオンと錯体を形成するとともに（例えば、下記概略反応式（ＩＩ））、ホスホン酸化合物部分に含まれる窒素原子がその非共有電子対により、金属基材表面との吸着作用を発揮する。しかも、ホスホン酸化合物錯体の存在により、皮膜の非晶質化が促進され、皮膜の金属基材表面に対する柔軟性および密着性が向上する。これらの結果、非導電性および密着性に優れた保護皮膜が形成され、耐食性がより十分に向上するものと考えられる。なお、以下の概略反応式は保護皮膜の形成に係わる主要な物質に由来する生成物の形成を概略的に示すものである。 At the time of forming the protective film, the phosphate ion of the phosphate compound is reacted with the ion of the metal A having a high ionization tendency contained in the plating layer (for example, the following general reaction formula (I)), thereby forming the main skeleton of the film. A non-conductive compound is produced as a component. On the other hand, the phosphonic acid compound forms a complex with the ion of metal A having a high ionization tendency (for example, the following general reaction formula (II)), and the nitrogen atom contained in the phosphonic acid compound portion is caused by the unshared electron pair. Exhibits an adsorption action with the surface of the metal substrate. Moreover, the presence of the phosphonic acid compound complex promotes the amorphization of the film, and improves the flexibility and adhesion of the film to the surface of the metal substrate. As a result, it is considered that a protective film excellent in non-conductivity and adhesion is formed, and the corrosion resistance is more sufficiently improved. In addition, the following general reaction formula schematically shows formation of a product derived from a main substance related to formation of a protective film.
本明細書中、耐食性とは、腐食に抵抗する特性のことであり、特に欠陥が形成されて金属基材が露出しても、腐食に対して十分に抵抗し得る特性のことである。耐食性は自己修復性を包含する概念で用いるものとする。自己修復性とは、欠陥の形成により金属基材が露出しても、当該露出した金属基材の表面に保護皮膜が形成されることにより、欠陥を修復するような挙動を示す特性のことである。 In this specification, the corrosion resistance is a characteristic that resists corrosion, and is a characteristic that can sufficiently resist corrosion even when a defect is formed and a metal substrate is exposed. Corrosion resistance shall be used in a concept that includes self-healing properties. Self-healing is a characteristic that even if a metal substrate is exposed due to the formation of a defect, a protective film is formed on the surface of the exposed metal substrate, thereby exhibiting a behavior that repairs the defect. is there.
本発明の修復剤は、保護皮膜の形成促進の観点から、イオン化傾向が高い金属を含有する化合物をさらに含むことが好ましい。以下、修復剤に含まれるこのような化合物に含有されるイオン化傾向が高い金属を、前記めっき層に含まれるイオン化傾向が高い金属Ａと区別して、「イオン化傾向が高い金属Ｂ」ということがある。このようなイオン化傾向が高い金属Ｂも、イオンの形態で、保護皮膜の形成に寄与する。イオン化傾向が高い金属Ｂは、前記したイオン化傾向が高い金属Ａと同様の範囲内の金属から選択されればよく、好ましくはイオン化傾向が高い金属Ａと同種の金属である。 It is preferable that the restoration | repair agent of this invention further contains the compound containing the metal with a high ionization tendency from a viewpoint of formation of a protective film. Hereinafter, a metal having a high ionization tendency contained in such a compound contained in the restorative agent may be referred to as “metal B having a high ionization tendency” in distinction from a metal A having a high ionization tendency contained in the plating layer. . Such a metal B having a high ionization tendency also contributes to the formation of a protective film in the form of ions. The metal B having a high ionization tendency may be selected from metals in the same range as the metal A having a high ionization tendency, and is preferably the same type of metal as the metal A having a high ionization tendency.
イオン化傾向が高い金属Ｂは、水中において当該金属がイオンの形態で存在できる限り特に限定されず、例えば、亜鉛、鉄、マグネシウム、コバルト、ニッケル、クロム、銀、ジルコニウム、アルミニウム等が挙げられる。水中での錯体の形成の観点、特にＡＴＭＰとの錯体の形成の観点から、これらの金属のうち、２価〜４価（望ましくは２価および４価）の金属、特に亜鉛、鉄、ニッケル、ジルコニウムが好ましく、亜鉛がより好ましい。イオン化傾向が高い金属Ｂを含有する化合物は、水中において当該金属がイオンの形態で存在できる限り特に限定されない。イオン化傾向が高い金属Ｂを含有する化合物の好ましい具体例として、例えば、硫酸亜鉛、硫酸鉄、硫酸ニッケル、硫酸ジルコニウム、硝酸亜鉛、硫酸アルミニウム、硝酸アルミニウム、硫酸マグネシウム、硝酸マグネシウム等が挙げられる。 The metal B having a high ionization tendency is not particularly limited as long as the metal can exist in the form of ions in water, and examples thereof include zinc, iron, magnesium, cobalt, nickel, chromium, silver, zirconium, and aluminum. From the viewpoint of forming a complex in water, particularly from the viewpoint of forming a complex with ATMP, among these metals, divalent to tetravalent (preferably divalent and tetravalent) metals, particularly zinc, iron, nickel, Zirconium is preferred and zinc is more preferred. The compound containing metal B having a high ionization tendency is not particularly limited as long as the metal can exist in the form of ions in water. Preferable specific examples of the compound containing metal B having a high ionization tendency include, for example, zinc sulfate, iron sulfate, nickel sulfate, zirconium sulfate, zinc nitrate, aluminum sulfate, aluminum nitrate, magnesium sulfate, magnesium nitrate and the like.
イオン化傾向が高い金属Ｂを含有する化合物は、リン酸化合物と前記ホスホン酸化合物との合計量１００重量部に対して１０〜４００重量部で含有されることが好ましく、保護皮膜の形成促進の観点から、特に好ましくは３０〜３００重量部、より好ましくは８０〜３００重量部、さらに好ましくは８０〜２００重量部、最も好ましくは１１０〜１５０重量部で含有される。イオン化傾向が高い金属Ｂを含有する化合物は２種以上の化合物を使用してもよく、その場合、それらの合計量が上記範囲内であればよい。 The compound containing metal B having a high ionization tendency is preferably contained in an amount of 10 to 400 parts by weight with respect to 100 parts by weight of the total amount of the phosphoric acid compound and the phosphonic acid compound. From 30 to 300 parts by weight, more preferably from 80 to 300 parts by weight, still more preferably from 80 to 200 parts by weight, and most preferably from 110 to 150 parts by weight. Two or more kinds of compounds may be used as the compound containing metal B having a high ionization tendency, and in this case, the total amount thereof may be within the above range.
［めっき基材の修復方法（修復剤の使用方法）］
本発明は、前記した修復剤を用いて、めっき基材を修復する方法も提供する。
[Repair method of plating base material (How to use repair agent)]
The present invention also provides a method of repairing a plating substrate using the above-described repairing agent.
めっき基材の修復方法においては、修復剤は、めっき層に予め含まれていてもよいし、または水溶液として別途、使用されてもよい。 In the repair method of the plating base material, the repair agent may be previously contained in the plating layer, or may be used separately as an aqueous solution.
修復剤をめっき層に予め含有させる場合、例えば、前記した衝撃めっき法において、被処理物（金属基材１）に投射される複合粒子の外郭部の構成金属粒子におけるさらに外郭部に修復剤を付着させておく。これにより、図２に示すように、めっき層２において構成金属粒子２１の界面および間隙に修復剤３０を存在させることができる。図２のめっき層２中、修復剤３０は黒丸で示されているが、これに限定されるものではなく、例えば、構成金属粒子２１の表面に層状に存在していてもよい。このような場合における修復剤の含有量は通常、めっき層全量に対して、０．１５〜１８．２０重量％であり、好ましくは０．５０〜７．７０重量％である。 When the restoration agent is preliminarily contained in the plating layer, for example, in the above-described impact plating method, the restoration agent is further added to the outer portion of the constituent metal particles of the outer portion of the composite particle projected onto the object to be processed (metal substrate 1). Leave it attached. Thereby, as shown in FIG. 2, the repairing agent 30 can be present in the interface and the gap of the constituent metal particles 21 in the plating layer 2. In the plating layer 2 of FIG. 2, the restoration agent 30 is indicated by a black circle, but is not limited thereto, and may be present in a layered manner on the surface of the constituent metal particles 21, for example. In such a case, the content of the restoration agent is usually 0.15 to 18.20% by weight, preferably 0.50 to 7.70% by weight, based on the total amount of the plating layer.
この場合、めっき基材１０に、図２に示すような金属基材１に達する欠陥１３が形成されたら、前記めっき層２に含有されるイオン化傾向が高い金属、リン酸化合物およびホスホン酸化合物が金属基材１の露出表面に滲出および移動する。その結果、保護皮膜１４が形成される。金属基材１の露出表面に滲出するイオン化傾向が高い金属は、めっき層２を構成するイオン化傾向が高い金属Ａであってもよいし、または当該イオン化傾向が高い金属Ａと、修復剤に含まれるイオン化傾向が高い金属Ｂを含有する化合物に由来するものとの混合物であってもよい。保護皮膜１４を構成する材料（すなわちイオン化傾向が高い金属、リン酸化合物およびホスホン酸化合物）の滲出および移動は、欠陥１３に付着する水分（例えば雨水）により達成されてもよいし、空気中の水分により達成されてもよいし、または欠陥１３が形成されためっき基材１０を水中に浸漬することにより達成されてもよい。 In this case, when the defect 13 reaching the metal substrate 1 as shown in FIG. 2 is formed on the plating substrate 10, the metal, phosphate compound, and phosphonic acid compound having a high ionization tendency contained in the plating layer 2 are formed. It exudes and moves to the exposed surface of the metal substrate 1. As a result, the protective film 14 is formed. The metal having a high ionization tendency that oozes on the exposed surface of the metal substrate 1 may be the metal A having a high ionization tendency that constitutes the plating layer 2, or the metal A having a high ionization tendency and the restoration agent. It may be a mixture with a compound derived from a compound containing metal B having a high ionization tendency. Exudation and movement of the material constituting the protective film 14 (that is, a metal, a phosphoric acid compound and a phosphonic acid compound having a high ionization tendency) may be achieved by moisture (for example, rainwater) adhering to the defect 13 or in the air. It may be achieved by moisture, or may be achieved by immersing the plating substrate 10 on which the defect 13 is formed in water.
修復剤をめっき層に予め含有させる場合、また例えば、修復剤の溶液をめっき層２の表面に塗布し、乾燥することにより、図３に示すように、めっき層２の表面に修復剤３０の層を形成してもよい。このとき、図３には示されていないが、修復剤３０は、図２に示すように、構成金属粒子２１の界面および間隙にも存在してもよい。溶液を構成する溶媒は、修復剤の全成分を溶解できる限り特に限定されず、水であってもよいし、または有機溶剤であってもよい。このような場合の修復剤の含有量は通常、修復剤をめっき層の構成金属粒子の界面および間隙に存在させる上記の場合と同様の範囲内である。 When the restoration agent is preliminarily contained in the plating layer, for example, by applying a solution of the restoration agent to the surface of the plating layer 2 and drying, the surface of the plating layer 2 is coated with the restoration agent 30 as shown in FIG. A layer may be formed. At this time, although not shown in FIG. 3, the repairing agent 30 may also exist at the interface and gaps of the constituent metal particles 21 as shown in FIG. 2. The solvent constituting the solution is not particularly limited as long as all the components of the restoration agent can be dissolved, and may be water or an organic solvent. In such a case, the content of the restoration agent is usually in the same range as in the above case where the restoration agent is present at the interface and gap between the constituent metal particles of the plating layer.
この場合、めっき基材１０に、図３に示すような金属基材１に達する欠陥１３が形成されたら、前記めっき層２に含有されるイオン化傾向が高い金属、リン酸化合物およびホスホン酸化合物が金属基材１の露出表面に移動する。その結果、保護皮膜１４が形成される。金属基材１の露出表面に移動するイオン化傾向が高い金属は、めっき層２を構成するイオン化傾向が高い金属Ａであってもよいし、または当該イオン化傾向が高い金属Ａと、修復剤に含まれるイオン化傾向が高い金属Ｂを含有する化合物に由来するものとの混合物であってもよい。保護皮膜１４を構成する材料（すなわちイオン化傾向が高い金属、リン酸化合物およびホスホン酸化合物）の移動は、欠陥１３に付着する水分（例えば雨水）により達成されてもよいし、空気中の水分により達成されてもよいし、または欠陥１３が形成されためっき基材１０を水中に浸漬することにより達成されてもよい。 In this case, when the defect 13 reaching the metal substrate 1 as shown in FIG. 3 is formed on the plating substrate 10, the metal, phosphate compound, and phosphonic acid compound, which are contained in the plating layer 2 and have a high ionization tendency, are present. It moves to the exposed surface of the metal substrate 1. As a result, the protective film 14 is formed. The metal having a high ionization tendency that moves to the exposed surface of the metal substrate 1 may be the metal A having a high ionization tendency constituting the plating layer 2, or the metal A having a high ionization tendency and included in the repairing agent. It may be a mixture with a compound derived from a compound containing metal B having a high ionization tendency. The movement of the material constituting the protective film 14 (that is, a metal having a high ionization tendency, a phosphoric acid compound, and a phosphonic acid compound) may be achieved by moisture adhering to the defect 13 (for example, rainwater), or by moisture in the air. It may be achieved, or may be achieved by immersing the plating substrate 10 on which the defect 13 is formed in water.
修復剤がめっき基材とは別に水溶液として使用される場合、めっき基材に金属基材に達する欠陥が形成されたら、図４に示すように、修復剤の水溶液３１を当該欠陥１３に接触させる。これにより、めっき層２に含有されるイオン化傾向が高い金属Ａが金属基材の露出表面に滲出する。このとき、水溶液中の修復剤に含まれる前記リン酸化合物および前記ホスホン酸化合物、ならびに所望によりイオン化傾向が高い金属Ｂが金属基材の露出表面に移動する。その結果、イオン化傾向が高い金属、前記リン酸化合物および前記ホスホン酸化合物が金属基材の露出表面に保護皮膜を形成する。保護皮膜１４を構成する材料（すなわちイオン化傾向が高い金属、リン酸化合物およびホスホン酸化合物）の滲出および移動は、当該材料が修復剤水溶液中を移動することにより達成される。図４の水溶液３１中、修復剤３０は黒丸で分散されているが、通常は水溶液中に溶解されている。 When the restoration agent is used as an aqueous solution separately from the plating base material, when a defect reaching the metal base material is formed on the plating base material, the aqueous solution 31 of the restoration agent is brought into contact with the defect 13 as shown in FIG. . Thereby, the metal A with a high ionization tendency contained in the plating layer 2 exudes to the exposed surface of the metal substrate. At this time, the phosphoric acid compound and the phosphonic acid compound contained in the restoration agent in the aqueous solution and, if desired, the metal B having a high ionization tendency move to the exposed surface of the metal substrate. As a result, the metal having a high ionization tendency, the phosphoric acid compound, and the phosphonic acid compound form a protective film on the exposed surface of the metal substrate. Exudation and movement of the material constituting the protective film 14 (that is, a metal, a phosphoric acid compound, and a phosphonic acid compound having a high ionization tendency) are achieved by the movement of the material in the aqueous repair agent solution. In the aqueous solution 31 of FIG. 4, the restoration agent 30 is dispersed with black circles, but is usually dissolved in the aqueous solution.
図４において、修復剤の水溶液３１と欠陥１３との接触は、当該欠陥１３に修復剤の水溶液３１を塗布することにより達成されているが、これに限定されず、例えば、当該欠陥を有するめっき基材を修復剤の水溶液に浸漬することにより達成されてもよい。 In FIG. 4, the contact between the repair agent aqueous solution 31 and the defect 13 is achieved by applying the repair agent aqueous solution 31 to the defect 13. However, the present invention is not limited to this, for example, plating having the defect. It may be achieved by immersing the substrate in an aqueous solution of a repair agent.
このような場合における水溶液中の修復剤の濃度（全成分の合計濃度）は１００ｐｐｍ以上、特に５００ｐｐｍ以上であり、好ましくは５００〜１００００ｐｐｍ、より好ましくは８００〜１００００ｐｐｍである。ｐｐｍは重量基準の割合の単位である。 In such a case, the concentration of the restoration agent (total concentration of all components) in the aqueous solution is 100 ppm or more, particularly 500 ppm or more, preferably 500 to 10000 ppm, more preferably 800 to 10000 ppm. ppm is a unit of weight-based proportion.
本発明のめっき基材の修復方法において、保護皮膜１３は金属基材１の露出表面に選択的に形成される。これは、特定の理論に拘束されることを意図するわけではないが、以下の理由によるものと考えられる。
（１）金属基材１は初期に腐食電位（負）を有するため、イオン化傾向が高い金属が正イオンとして金属基材１の露出表面に静電気的に引き寄せられると、保護皮膜の他の構成材料も静電気的に当該正イオンに引き寄せられる。
（２）引き寄せられたイオンは金属基材１の表面に吸着した後に、相互に結合し、皮膜を形成する。これらは２次元、あるいは３次元膜を形成すると同時に、金属基材１の表面とに強く吸着あるいは結合し、密着性の高い皮膜となる。
In the plating substrate repair method of the present invention, the protective film 13 is selectively formed on the exposed surface of the metal substrate 1. This is not intended to be bound by any particular theory, but may be due to the following reasons.
(1) Since the metal substrate 1 initially has a corrosion potential (negative), when a metal having a high ionization tendency is electrostatically attracted to the exposed surface of the metal substrate 1 as positive ions, other constituent materials of the protective coating Is also electrostatically attracted to the positive ions.
(2) The attracted ions are adsorbed on the surface of the metal substrate 1 and then bonded to each other to form a film. These form a two-dimensional or three-dimensional film and at the same time strongly adsorb or bond to the surface of the metal substrate 1 to form a highly adhesive film.
保護皮膜１４が金属基材１の露出表面に形成されていることは、当該表面のＳＥＭ写真によっても、または当該表面にある皮膜のＸＲＤ（Ｘ線回折法）による分析によっても、容易に確認することができる。 The formation of the protective film 14 on the exposed surface of the metal substrate 1 can be easily confirmed by an SEM photograph of the surface or by analysis of the film on the surface by XRD (X-ray diffraction method). be able to.
本明細書中、欠陥１３はめっき層２の表面から金属基材１に達する深さを有するものであり、引っかき傷（スクラッチ）ともいう。 In the present specification, the defect 13 has a depth reaching the metal substrate 1 from the surface of the plating layer 2 and is also referred to as a scratch.
[実験例Ａ]
（実施例Ａ１）
図５に示す装置５０において、炭素鋼板（ハイテン材料）（１２ｍｍ×１２ｍｍ）（含有割合：炭素０．５重量％、ケイ素０．０２重量％、マンガン０．２重量％、リン０．１重量％、硫黄０．１重量％、残部；鉄）を作用電極５１として、空気飽和させた試験液（３５℃）５２に２４時間浸漬して、自然電位を計測した。試験液は、塩化ナトリウム水溶液に、修復剤として、リン酸二水素ナトリウム、ＡＴＭＰおよび硫酸亜鉛を溶解して調製した。塩化ナトリウム濃度は０．５重量％、リン酸二水素ナトリウム濃度は５００ｐｐｍ、ＡＴＭＰ濃度は５００ｐｐｍおよび硫酸亜鉛濃度は５００ｐｐｍであった。試験液はＮａＯＨ／ＨＣｌによりｐＨ６．２に調整した。対極５３としては白金電極を、参照電極５４としてはＡｇ／ＡｇＣｌ電極を用いた。
[Experiment A]
(Example A1)
In the apparatus 50 shown in FIG. 5, carbon steel plate (high tensile material) (12 mm × 12 mm) (content ratio: carbon 0.5 wt%, silicon 0.02 wt%, manganese 0.2 wt%, phosphorus 0.1 wt%) Sulfur 0.1 wt%, balance: iron) was immersed in a test solution (35 ° C.) 52 saturated with air as a working electrode 51 for 24 hours, and the natural potential was measured. The test solution was prepared by dissolving sodium dihydrogen phosphate, ATMP and zinc sulfate as a restoration agent in an aqueous sodium chloride solution. The sodium chloride concentration was 0.5% by weight, the sodium dihydrogen phosphate concentration was 500 ppm, the ATMP concentration was 500 ppm, and the zinc sulfate concentration was 500 ppm. The test solution was adjusted to pH 6.2 with NaOH / HCl. A platinum electrode was used as the counter electrode 53, and an Ag / AgCl electrode was used as the reference electrode 54.
次いで、作用電極５１を試験液５２に浸漬したまま、作用電極５１の電位をポテンショスタット５５により変化させながら、作用電極５１でカソード分極を行い、カソード電流値を測定した。得られた電流−電位曲線の一例を図６に示した。図６に、本実施例の電流−電位曲線を「ＡＴＭＰ＋ＮａＨ２ＰＯ４＋ＺｎＳＯ４」として示した。図６において、−０．８Ｖおよび−１．１Ｖのときの電流抑制率Ｅを算出した。 Next, while the working electrode 51 was immersed in the test solution 52, cathode polarization was performed at the working electrode 51 while changing the potential of the working electrode 51 with a potentiostat 55, and the cathode current value was measured. An example of the obtained current-potential curve is shown in FIG. FIG. 6 shows the current-potential curve of this example as “ATMP + NaH 2 PO 4 + ZnSO 4 ”. In FIG. 6, the current suppression rate E at −0.8V and −1.1V was calculated.
電流抑制率は以下の式に基づいて算出した。
Ｉ０は試験液に修復剤を添加しなかったときの電流密度であって、具体的には後述の比較例Ａ１において修復剤を添加しなかったときの電流密度である。
Ｉは試験液に本実施例の修復剤を添加したときの電流密度であって、本実施例で測定された電流密度である。
I 0 is the current density when no restoration agent is added to the test solution, and specifically, the current density when no restoration agent is added in Comparative Example A1 described later.
I is the current density when the restoration agent of this example is added to the test solution, and is the current density measured in this example.
修復剤の添加によるカソード電流値の低下は、露出した金属基材表面での保護皮膜の形成を意味し、当該修復剤が耐食性、特に自己修復性を有していることを示す。 The decrease in the cathode current value due to the addition of the restoration agent means the formation of a protective film on the exposed metal substrate surface, which indicates that the restoration agent has corrosion resistance, particularly self-healing properties.
（比較例Ａ１〜Ａ３４）
試験液に所定の化合物を所定の量で溶解させたこと以外、実施例Ａ１と同様の方法により、カソード電流値を測定し、電流抑制率Ｅを算出した。各比較例における化合物の種類および量を以下の表に示した。電流抑制率を測定するための電位は−０．８Ｖおよび−１．１Ｖのときであった。図６に、比較例Ａ１の電流−電位曲線を「Ｐｌａｉｎ」として、比較例Ａ５の電流−電位曲線を「ＮａＨ２ＰＯ４」として、比較例Ａ６の電流−電位曲線を「ＺｎＳＯ４」として、比較例Ａ２６の電流−電位曲線を「ＡＴＭＰ」として示した。
(Comparative Examples A1 to A34)
The cathode current value was measured in the same manner as in Example A1 except that a predetermined compound was dissolved in a predetermined amount in the test solution, and a current suppression rate E was calculated. The types and amounts of the compounds in each comparative example are shown in the following table. The potential for measuring the current suppression rate was -0.8V and -1.1V. 6, the current-potential curve of Comparative Example A1 is “Plain”, the current-potential curve of Comparative Example A5 is “NaH 2 PO 4 ”, and the current-potential curve of Comparative Example A6 is “ZnSO 4 ”. The current-potential curve of Comparative Example A26 is shown as “ATMP”.
実施例Ａ１および比較例Ａ１、Ａ１８、Ａ２４およびＡ２８において、カソード電流値測定後の作用電極表面のＳＥＭ写真を撮影し、それぞれ図７〜図１１に示した。試験液への浸漬前の作用電極表面のＳＥＭ写真を撮影し、図１２に示した。
これらの結果から、本発明の修復剤は金属基材表面に、密着性に優れた保護皮膜を形成することにより、カソード電流抑制率に優れた保護皮膜、すなわち酸素および水素の還元反応を抑制する優れた保護皮膜を形成することが明らかとなった。
In Example A1 and Comparative Examples A1, A18, A24, and A28, SEM photographs of the surface of the working electrode after measuring the cathode current value were taken and shown in FIGS. 7 to 11, respectively. A SEM photograph of the working electrode surface before immersion in the test solution was taken and shown in FIG.
From these results, the restoration agent of the present invention forms a protective film with excellent adhesion on the surface of the metal substrate, thereby suppressing the reduction reaction of oxygen and hydrogen with a protective film with excellent cathode current suppression rate. It was revealed that an excellent protective film was formed.
（実施例Ａ２）
試験液の塩化ナトリウム濃度を３．５重量％としたこと以外、実施例Ａ１と同様の方法により、カソード分極を行った。カソード分極後の作用電極表面の保護皮膜を熱重量分析（ＴＧ）に供した。その結果を図１３に示した。
(Example A2)
Cathodic polarization was performed in the same manner as in Example A1, except that the sodium chloride concentration of the test solution was 3.5% by weight. The protective film on the surface of the working electrode after cathodic polarization was subjected to thermogravimetric analysis (TG). The results are shown in FIG.
（比較例Ａ３５）
試験液の塩化ナトリウム濃度を３．５重量％としたこと以外、比較例Ａ１８と同様の方法により、カソード分極を行った。カソード分極後の作用電極表面の保護皮膜を熱重量分析（ＴＧ）に供した。その結果を図１３に示した。
(Comparative Example A35)
Cathodic polarization was performed in the same manner as in Comparative Example A18, except that the sodium chloride concentration in the test solution was 3.5% by weight. The protective film on the surface of the working electrode after cathodic polarization was subjected to thermogravimetric analysis (TG). The results are shown in FIG.
［実験例Ｂ］
（実施例Ｂ１〜Ｂ１０および比較例Ｂ１〜Ｂ６）
試験液に所定の化合物を所定の量で溶解させたこと以外、実施例Ａ１と同様の方法により、カソード電流値を測定し、電流抑制率Ｅを算出した。各実施例／比較例における化合物の種類および量を以下の表に示した。
[Experiment B]
(Examples B1 to B10 and Comparative Examples B1 to B6)
The cathode current value was measured in the same manner as in Example A1 except that a predetermined compound was dissolved in a predetermined amount in the test solution, and a current suppression rate E was calculated. The types and amounts of the compounds in each Example / Comparative Example are shown in the following table.
電流抑制率Ｅのランク付けは以下の方法に従った。
（−０．８Ｖ）
Ｓ：Ｅ＝８５％以上；
Ａ：Ｅ＝８０％以上；
Ｂ：Ｅ＝７５％以上；
Ｃ：Ｅ＝７０％以上（実用上問題なし）；
Ｄ：Ｅ＝７０％未満（実用上問題あり）。
The current suppression rate E was ranked according to the following method.
(-0.8V)
S: E = 85% or more;
A: E = 80% or more;
B: E = 75% or more;
C: E = 70% or more (no problem in practical use);
D: E = less than 70% (practical problem).
（−１．２Ｖ）
Ｓ：Ｅ＝９１％以上；
Ａ：Ｅ＝８８％以上；
Ｂ：Ｅ＝８５％以上；
Ｃ：Ｅ＝７６％以上（実用上問題なし）；
Ｄ：Ｅ＝７６％未満（実用上問題あり）。
(-1.2V)
S: E = 91% or more;
A: E = 88% or more;
B: E = 85% or more;
C: E = 76% or more (no problem in practical use);
D: E = less than 76% (practical problem).
実施例Ｂ１および比較例Ｂ４において、カソード電流値測定後の作用電極表面のＳＥＭ写真を撮影し、それぞれ図１４および図１４に示した。また当該作用電極表面に形成されていた保護皮膜をＸＲＤ（Ｘ線回折法）による分析に供し、結果を図１５に示した。これらの結果から、ＡＴＭＰの添加は、Ｚｎ３（ＰＯ４）２・４Ｈ２Ｏのピークを消失させ、非晶質構造の形成を促進させるものと考えられる。 In Example B1 and Comparative Example B4, SEM photographs of the surface of the working electrode after measuring the cathode current value were taken and shown in FIGS. 14 and 14, respectively. Further, the protective film formed on the surface of the working electrode was subjected to analysis by XRD (X-ray diffraction method), and the result is shown in FIG. From these results, it is considered that the addition of ATMP eliminates the Zn 3 (PO 4 ) 2 .4H 2 O peak and promotes the formation of an amorphous structure.
［実験例Ｃ：電流測定率Ｅの測定時における電位の決定方法］
（参考例Ｃ１）
空気飽和させる代わりに、窒素飽和させた以外、比較例Ａ１と同様の方法により、カソード電流値を測定し、電流−電位曲線を得た。図１６に、参考例Ｃ１の電流−電位曲線を「Ｎ２」として、比較例Ａ１の電流−電位曲線を「Ａｉｒ」として示した。これらの結果より、酸素の還元反応が優位に起こるのは−０．８Ｖ近傍であり、水素の還元反応が優位に起こるのは−１．１Ｖであるため、電流測定率Ｅの算出時における電位はそれぞれの電位の近傍に決定した。
[Experimental example C: Method for determining potential when measuring current measurement rate E]
(Reference Example C1)
A cathode current value was measured in the same manner as in Comparative Example A1 except that nitrogen was saturated instead of air saturation, and a current-potential curve was obtained. FIG. 16 shows the current-potential curve of Reference Example C1 as “N 2 ” and the current-potential curve of Comparative Example A1 as “Air”. From these results, the oxygen reduction reaction preferentially occurs in the vicinity of −0.8 V, and the hydrogen reduction reaction preferentially occurs in −1.1 V. Therefore, the potential when calculating the current measurement rate E is calculated. Was determined in the vicinity of each potential.
本発明の修復剤は、めっき基材に形成された欠陥の修復に有用である。 The repairing agent of the present invention is useful for repairing defects formed on the plating substrate.
１：金属基材
２：めっき層
１０：めっき基材
１３：欠陥（引っかき傷）
１４：保護皮膜
３０：修復剤
1: Metal base material 2: Plating layer 10: Plating base material 13: Defect (scratch)
14: Protective film 30: Restoring agent
Claims (23)
リン酸化合物およびホスホン酸化合物を含む修復剤。 A repair agent for a plating substrate having a plating layer containing a metal having a higher ionization tendency than the metal constituting the metal substrate on the surface of the metal substrate,
A restoration agent comprising a phosphoric acid compound and a phosphonic acid compound.
前記イオン化傾向が高い金属、前記リン酸化合物および前記ホスホン酸化合物が露出した金属基材の表面に保護皮膜を形成する、請求項１または２に記載の修復剤。 The plating substrate has a defect reaching the metal substrate;
The restoration | repair agent of Claim 1 or 2 which forms a protective film on the surface of the metal base material which the said metal with high ionization tendency, the said phosphoric acid compound, and the said phosphonic acid compound exposed.
前記陽イオンが、１価金属イオン、２価金属イオン、３価金属イオンおよびアンモニウムイオンからなる群から選択される１種以上のイオンである、請求項８に記載の修復剤。 The phosphate is a salt of a first phosphate ion (H 2 PO 4 − ), a second phosphate ion (HPO 4 2− ) or a third phosphate ion (PO 4 3− ) and a cation. Yes,
The restoration agent according to claim 8, wherein the cation is one or more ions selected from the group consisting of a monovalent metal ion, a divalent metal ion, a trivalent metal ion, and an ammonium ion.
前記めっき層が鉄よりもイオン化傾向が高い金属を含有する、請求項１〜１２のいずれかに記載の修復剤。 The metal substrate is a steel plate;
The restoration | repair agent in any one of Claims 1-12 in which the said plating layer contains the metal whose ionization tendency is higher than iron.
前記めっき基材に前記金属基材に達する欠陥が形成されたら、前記めっき層に含有される前記イオン化傾向が高い金属、前記リン酸化合物および前記ホスホン酸化合物が露出した金属基材の表面に滲出して保護皮膜を形成する、請求項１６に記載の修復方法。 The restoration agent is included in the plating layer in advance,
When a defect reaching the metal base is formed on the plating base, the metal contained in the plating layer has a high ionization tendency, the phosphate compound, and the phosphonic acid compound are exuded on the exposed surface of the metal base. The repair method according to claim 16, wherein a protective film is formed.
前記修復剤がリン酸化合物およびホスホン酸化合物を含む、めっき基材。 A plating substrate having a plating layer containing a metal and a restoration agent having a higher ionization tendency than the metal constituting the metal substrate on the surface of the metal substrate,
The plating base material in which the said restoration | repair agent contains a phosphoric acid compound and a phosphonic acid compound.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016159221A JP2018028115A (en) | 2016-08-15 | 2016-08-15 | Agent and method for repairing plating base material, and plating base material |
| US15/667,972 US20180044797A1 (en) | 2016-08-15 | 2017-08-03 | Repair agent and repair method for plated base, as well as plated base |
| CN201710672410.4A CN107761103B (en) | 2016-08-15 | 2017-08-08 | The renovation agent of plating base, the restorative procedure of plating base and plating base |
| DE102017118413.9A DE102017118413A1 (en) | 2016-08-15 | 2017-08-11 | Means and methods for repairing coated base material and coated base material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2016159221A JP2018028115A (en) | 2016-08-15 | 2016-08-15 | Agent and method for repairing plating base material, and plating base material |
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| Publication Number | Publication Date |
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| JP2018028115A true JP2018028115A (en) | 2018-02-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2016159221A Pending JP2018028115A (en) | 2016-08-15 | 2016-08-15 | Agent and method for repairing plating base material, and plating base material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20180044797A1 (en) |
| JP (1) | JP2018028115A (en) |
| CN (1) | CN107761103B (en) |
| DE (1) | DE102017118413A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019188743A (en) * | 2018-04-27 | 2019-10-31 | 国立大学法人広島大学 | Restorable plating substrate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220307151A1 (en) * | 2021-03-29 | 2022-09-29 | Suat Sen | Control of texture and morphology of zinc films through pulsed methods from additive-free electrolytes |
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| JP2002348675A (en) * | 2001-05-25 | 2002-12-04 | Nippon Steel Corp | Zinc-base plated steel sheet superior in corrosion resistance after working, corrosion resistance after heating, and galling resistance |
| JP2009068115A (en) * | 1999-04-12 | 2009-04-02 | Toyo Kohan Co Ltd | Production method of surface-treated steel sheet, surface-treated steel sheet and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin |
| JP2010248600A (en) * | 2009-04-20 | 2010-11-04 | Sumitomo Metal Ind Ltd | Surface treated steel sheet, method for manufacturing surface treated steel sheet, and casing obtained from the steel sheet |
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| JP2010174273A (en) | 2009-01-27 | 2010-08-12 | Hiroshima Univ | Corrosion-preventing film and corrosion-resistant metal material |
| US10697067B2 (en) * | 2015-02-03 | 2020-06-30 | Nippon Steel Corporation | Steel sheet for a fuel tank |
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2016
- 2016-08-15 JP JP2016159221A patent/JP2018028115A/en active Pending
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2017
- 2017-08-03 US US15/667,972 patent/US20180044797A1/en not_active Abandoned
- 2017-08-08 CN CN201710672410.4A patent/CN107761103B/en not_active Expired - Fee Related
- 2017-08-11 DE DE102017118413.9A patent/DE102017118413A1/en not_active Ceased
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| JP2009068115A (en) * | 1999-04-12 | 2009-04-02 | Toyo Kohan Co Ltd | Production method of surface-treated steel sheet, surface-treated steel sheet and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin |
| JP2002348675A (en) * | 2001-05-25 | 2002-12-04 | Nippon Steel Corp | Zinc-base plated steel sheet superior in corrosion resistance after working, corrosion resistance after heating, and galling resistance |
| JP2010248600A (en) * | 2009-04-20 | 2010-11-04 | Sumitomo Metal Ind Ltd | Surface treated steel sheet, method for manufacturing surface treated steel sheet, and casing obtained from the steel sheet |
| JP2013227646A (en) * | 2012-03-27 | 2013-11-07 | Asahi Kagaku Kogyo Co Ltd | Surface treatment agent with excellent corrosion resistance for galvanized steel sheet, and galvanized steel sheet coated with the surface treatment agent |
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| JP2019188743A (en) * | 2018-04-27 | 2019-10-31 | 国立大学法人広島大学 | Restorable plating substrate |
| JP7077121B2 (en) | 2018-04-27 | 2022-05-30 | Ｎｏｆメタルコーティングス株式会社 | Repairable plating base material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107761103B (en) | 2019-08-09 |
| US20180044797A1 (en) | 2018-02-15 |
| CN107761103A (en) | 2018-03-06 |
| DE102017118413A1 (en) | 2018-02-15 |
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